JP2018188652A - Heat-resistant polyolefin compositions suitable for films - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide compositions that have characteristics of PVC-based formulations yet are free from PVC and its inherent disadvantages.SOLUTION: The compositions comprise: (1) a polymer selected from the group consisting of (A) an ethylene/α-olefin multiblock interpolymer, (B) a propylene based plastomer or elastomer, and (C) a mixture of (A) and (B); (2) about 1 to about 75 wt.% of a filler based on the weight of the composition; and (3) an effective amount of tackifier.SELECTED DRAWING: None

Description

The present invention relates to an improved polyolefin composition that is heat resistant and often suitable as a coating.

Polyvinyl chloride (PVC) is a widely used thermoplastic polymer. It is often used in applications that require compatible and / or flame resistant formulations. Examples of such applications include strips suitable for signboards, sagging cloths, and adhesive bandages. Unfortunately, PVC-based formulations often generate fumes and release HCl when burned. The released HCl fumes and the decomposition of the HCl fumes can cause health hazards. Furthermore, in order to obtain soft and easy to adapt properties to soft polyvinyl chloride (f-PVC), currently blending is done using phthalic acid, which leads to health risks. In addition, it is also disadvantageous that the production of polyvinyl chloride usually requires vinyl chloride starting materials. Production of vinyl chloride and incineration of PVC waste can generate harmful dioxins.
Accordingly, there is a need for a composition that does not have PVC and its inherent disadvantages while having properties such as PVC-based formulations.

Conveniently, compositions have been found that can replace PVC-based formulations and are often suitable, for example, as a coating. In one embodiment, the composition of the present invention comprises
(1) a polymer selected from the group consisting of (A) an ethylene / α-olefin multiblock interpolymer, (B) a propylene-based plastomer or elastomer, and (C) a mixture of (A) and (B);
(2) about 1 to about 75 weight percent filler, based on the weight of the composition;
(3) an effective amount of a tackifier;
including. In another embodiment, the ethylene / α-olefin multiblock interpolymer is characterized by one or more of the following properties before any cross-linking:
(1) an average block index greater than zero to about 1.0 and a molecular weight distribution Mw / Mn greater than about 1.3, or
(2) at least one molecular fraction that elutes at 40 ° C. to 130 ° C. when fractionated with TREF, having a block index of at least 0.5 and up to about 1, or ,
(3) Mw / Mn of about 1.7 to about 3.5, at least one melting point Tm (° C.) and density d
(G / cm ³ ), and the numerical values of Tm and d are
T _m > −6553.3 + 13735 (d) −7051.7 (d) ²
Tm and d corresponding to the relationship of
(4) Mw / Mn of about 1.7 to about 3.5, heat of fusion ΔH (J / g) and delta amount ΔT defined as the temperature difference between the maximum DSC peak and the maximum CRYSTAF peak ( ℃)
And the numerical values of ΔT and ΔH are ΔT> −0.1299 (ΔH) +62.81 (when ΔH is greater than zero and up to 130 J / g),
ΔT ≧ 48 ° C. (when ΔH is greater than 130 J / g),
And the CRYSTAF peak is measured using at least 5% cumulative polymer and if less than 5% of the polymer has a distinguishable CRYSTAF peak, CRYSTA
F temperature is 30 ° C. ΔT and ΔH, or
(5) Measured using a compression molded film of ethylene / α-olefin interpolymer,
300% strain and elastic recovery rate Re (%) in one cycle, and density d (g / cm ³ )
Where the values of Re and d are such that the ethylene / α-olefin interpolymer has substantially no cross-linked phase,
Re> 1481-1629 (d)
Re and d satisfying the relationship of
(6) A molecular fraction that elutes at 40 ° C. to 130 ° C. when fractionated with TREF, and is in an amount (−0.2013) T + 20.07 or more, more preferably in an amount (−0.2013) T + 21
. A fraction characterized in that it has a comonomer molar content of 07 or more and T is the numerical value of the peak elution temperature of the TREF fraction measured at ° C, or
(7) Storage elastic modulus G ′ at 25 ° C. (25 ° C.) and storage elastic modulus G ′ at 100 ° C. (100
G ′ (25 ° C.) and G ′ (100 ° C.) with a ratio of G ′ (25 ° C.): G ′ (100 ° C.) in the range of about 1: 1 to 9: 1.

Characteristics (1) to (7) of ethylene / α-olefin multiblock interpolymer
Is given before any significant cross-linking, ie to the ethylene / α-olefin interpolymer before cross-linking. The ethylene / α-olefin interpolymers useful in the present invention may or may not be cross-linked depending on the desired properties.
The use of properties (1) to (7) as measured before cross-linking is not intended to suggest that the interpolymer requires or does not require cross-linking, but is not significantly cross-linked. It suggests that the properties are measured with respect to the interpolymer. Cross-linking may or may not change each of these properties, depending on the specific polymer and degree of cross-linking.

Figure 5 shows the retention load (fraction) for 5 minutes when 100% strain is applied to the strip of control f-PVC and the strips of Formulations AD in Example 1. The recovery rate when the distortion with respect to the f-PVC control of Example 1 and formulations AD is removed is shown. Figure 2 shows the stress-strain curve of the inventive formulations AD of Example 1 and the f-PVC control. Figure 2 shows 25% hysteresis of f-PVC of Example 1 and formulations AD. The stress-strain curve of the flame-resistant compound 1-4 of this invention of Example 2 is shown. The retention load (fraction) for 5 minutes when 100% strain is applied to the formulations 1 to 4 of Example 2 is shown. The recovery rate when the distortion with respect to the formulations 1-4 of Example 2 was removed is shown. 2 shows the 25% hysteresis of Formulations 1-4 of Example 2. The melt strength is compared between Formulations 1 and 2 of Example 2 and Formulations 5 to 10 of Example 3. 2 shows the stress-strain curve of the flame resistant formulation of Example 5. The recovery rate when the distortion with respect to the formulation of Example 5 is removed is shown. The recovery rate when the distortion with respect to the formulation of Example 5 is removed is shown. Figure 3 shows tan delta versus temperature for the formulation of Example 5 with different amounts of tackifier.

“Polymer” means a polymer compound prepared by polymerizing the same or different monomers. The generic term “polymer” includes not only “interpolymer” but also the terms “homopolymer”, “copolymer” and “terpolymer”.

“Interpolymer” means a polymer that is prepared by polymerization of at least two different types of monomers. The generic term “interpolymer” refers to the term “copolymer” (usually used to refer to polymers prepared from two different monomers) and the term “terpolymer” (typically prepared from three different types of monomers). Used to refer to polymers). It also includes polymers made by polymerizing four or more types of monomers.

The term “composition” as used herein also includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the components or materials of the composition. Specifically included in the composition of the present invention is a graft wherein the initiator or coupling agent reacts with at least a portion of one or more polymers and / or at least a portion of one or more fillers. Or it is a coupled composition.

The compositions of the present invention typically include
(1) a polymer selected from the group consisting of (A) an olefin block copolymer, (B) a propylene-based plastomer or elastomer, and (C) a mixture of (A) and (B);
(2) about 0 weight percent to preferably about 1 weight percent to about 75 weight percent filler, based on the weight of the composition;
(3) an effective amount of a tackifier;
including.

“Olefin block copolymer” or “OBC” means an ethylene / α-olefin multiblock copolymer, comprising ethylene and one or more copolymerizable α-olefin comonomers in a polymerized form, having chemical or physical properties. Characterized by multiple blocks or segments of two or more different polymerized monomer units. The terms “interpolymer” and “copolymer” are used interchangeably herein. "Ethylene" in copolymers
Or when referring to the amount of “comonomer”, it should be understood to mean those polymerized units.
In some embodiments, the multi-block copolymer has the formula:
(AB) n
N is an integer of at least 1, preferably greater than 1, for example 2, 3, 4, 5
10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or more, “A” represents a hard block or segment and “B” represents a soft block or segment. Preferably, A and B are connected substantially linearly, and are different from being substantially branched or substantially star-shaped. In other embodiments, the A and B blocks are randomly distributed along the polymer chain. In other words, block copolymers usually do not have the following structure:
AAA-AA-BBB-BB.

In yet another embodiment, the block copolymer typically does not have a third type of block comprising different comonomers. In still other embodiments, each of block A and block B has monomers or comonomers that are substantially randomly distributed within the block. In other words, both block A and block B have two or more sub-segments (or sub-blocks) that differ in composition, such as a tip segment that differs substantially from the rest of the block.
Not included. For purposes of US patent practice, PCT Application No. PCT / US2005 / 008917 (Dow 63558D) filed March 17, 2005 is
Claims priority to US Provisional Application No. 60 / 553,906 filed on May 17, and International Publication No. WO2006 / 115839 published on November 2, 2006, the entire contents of which are incorporated by reference It shall be incorporated herein.

Preferably, the ethylene comprises the highest molar fraction of the entire block copolymer, i.e. ethylene comprises at least 50 mole percent of the entire polymer. More preferably, the ethylene is at least 60 mole percent, at least 70 mole percent, or at least 8
Containing 0 mole percent, a substantial remainder of the entire polymer preferably includes at least one other comonomer that is an alpha-olefin having 3 or more carbon atoms. In some embodiments, the olefin block copolymer may comprise 50 mol% to 90 mol%, preferably 60 mol% to 85 mol%, more preferably 65 mol% to 80 mol%. For many ethylene / octene block copolymers, preferred compositions have an ethylene content of 80 mole percent or more of the total polymer and 10 to 10 percent of the total polymer.
15 and preferably 15 to 20 mole percent octene content.

Olefin block copolymers contain various amounts of “hard” and “soft” segments. A “hard” segment is a block of polymerized units in which ethylene is present in an amount of up to 100 weight percent, greater than 95 weight percent or greater than 98 weight percent, based on the weight of the polymer. In other words, the comonomer content in the hard segment (content of monomers other than ethylene) is less than 5 weight percent or less than 2 weight percent based on the weight of the polymer, and may be as low as zero. In some embodiments, the hard segment includes all or substantially all units derived from ethylene. The “soft” segment has a comonomer content (content of monomers other than ethylene) of greater than 5 weight percent, greater than 8 weight percent, greater than 10 weight percent, or 15 weight based on the weight of the polymer. More than percent blocks of polymerized units. In some embodiments, the comonomer content in the soft segment is greater than 20 weight percent, greater than 25 weight percent, greater than 30 weight percent, greater than 35 weight percent, greater than 40 weight percent, There can be more than 45 weight percent, more than 50 weight percent, or more than 60 weight percent and up to 100 weight percent.

The soft segment in OBC is 1 to 99 weight percent of the total weight of OBC, or 5 to 95 weight percent, 10 to 90 weight percent, 15 to 85 weight percent of the total weight of OBC. Percent, 20 percent to 80 percent, 25 percent to 75 percent, 30 percent to 70 percent, 35 percent to 65 percent, 40 percent to 60 percent, or 45 percent to 55 percent by weight And can exist. Conversely, a hard segment may exist in a similar range. The soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR. Such methods and calculations are described in, for example, Colin L. et al.
P. Shan, Lonnie Hazlitt, et. al. March 1, 2006 in the name of
U.S. Pat. No. 7,608,668, filed 5 days "Ethylene / α-Olefin B"
lock Inter-polymers "and Dow Global Tec.
hnologies Inc. The entire disclosure of which is hereby incorporated by reference. In particular, the weight percentage and comonomer content of the hard and soft segments are described in US Pat. No. 7,608,668, columns 57-63.
It can be measured as described in the column.

The olefin block copolymer is preferably a polymer comprising two or more chemically distinct regions or segments (referred to as “blocks”) linked in a linear fashion, ie not pendant or grafted, but of polymerized ethylene functionality. From a point, it is a polymer containing chemically distinct units linked terminally to the terminal. In one embodiment, the block is of the amount or type of comonomer incorporated, density, amount of crystallinity, crystallite size, stereoregularity (isotactic or syndiotactic) of the polymer of such compositions. It varies in terms of type or degree, regioregularity or regioirregularity, amount of branching (including long chain branching or hyperbranching), uniformity, or any other chemical or physical property . Compared to prior art block interpolymers such as sequential monomer additions, flowable catalysts, or interpolymers produced by anionic polymerization, the OBC of the present invention, in one embodiment, combines with multiple catalysts in the preparation of the interpolymer. Depending on the effect of the transfer agent used, the polymer polydispersity of both block length distribution and / or block number distribution (P
DI or Mw / Mn or MWD) is a characteristic distribution.

In one embodiment, the OBC is produced in a continuous process, 1.7-3.5, or 1.8-
It has a polydispersity index, PDI of 3, or 1.8 to 2.5, or 1.8 to 2.2.
When produced in a batch or semi-batch process, the OBC has a PDI of 1.0-3.5, or 1.3-3, or 1.4-2.5, or 1.4-2.

In addition, the olefin block copolymer has a PDI that matches a Schulz Flory distribution rather than a Poisson distribution. The OBC of the present invention has both a polydisperse block distribution and a polydisperse distribution of block sizes. This results in a distinguishable polymer product with improved physical properties. The theoretical benefits of polydisperse block distributions are as follows: Potemkin,
Physical Review E (1998) 57 (6), pp. 6902-6912
And Dobrynin, J. et al. Chem. Phvs. (1997) 107 (21), p
Modeled and discussed in p9234-9238.

In one embodiment, the olefin block copolymers of the present invention have the most likely block length distribution. In one embodiment, the olefin block copolymer is defined as having:

(A) Mw / Mn of 1.7-3.5, at least one melting point Tm (° C.) and density d (g
/ Cm ³ ), and the numerical values of Tm and d are
Tm> −2002.9 + 4538.5 (d) −2422.2 (d) ²
Tm and d corresponding to the relationship of

(B) Mw / Mn of 1.7 to 3.5, each characterized by heat of fusion ΔH (J / g) and delta amount ΔT (° C.), where the delta amount ΔT is the maximum DSC peak and the maximum Defined as the temperature difference between the crystallization analysis fractionation (“CRYSTAF”) peaks, the values of ΔT and ΔH are
ΔT> −0.1299 (ΔH) +62.81 (when ΔH is greater than zero and up to 130 J / g),
ΔT ≧ 48 ° C. (when ΔH is greater than 130 J / g),
And the CRYSTAF peak is measured using at least 5% cumulative polymer and if less than 5% of the polymer has a distinguishable CRYSTAF peak, CRYSTA
F temperature is 30 ° C. ΔT and ΔH, and / or

(C) Measured using a compression molded film of ethylene / α-olefin interpolymer,
300% strain and elastic recovery rate Re (%) in one cycle, and density d (g / cm ³ )
(Here, the values of Re and d are determined when the ethylene / α-olefin interpolymer has substantially no crosslinked phase.
Re> 1481-1629 (d)
Re and d satisfying the relationship of

(D) A molecular fraction that elutes at 40 ° C. to 130 ° C. when fractionated using TREF, and is in an amount (−0.2013) T + 20.07 or more, more preferably in an amount (−0.2013) T + 21
. A fraction having a comonomer molar content of greater than or equal to 07 and wherein T is the numerical value of the peak elution temperature of the TREF fraction measured at 0 C, and / or

(E) Storage elastic modulus G ′ at 25 ° C. (25 ° C.) and storage elastic modulus G ′ at 100 ° C. (100
G ′ (25 ° C.) and G ′ (100 ° C.) with a ratio of G ′ (25 ° C.): G ′ (100 ° C.) in the range of about 1: 1 to 9: 1.

  The olefin block copolymer may also have the following:

(F) a molecular fraction that elutes at 40 ° C. to 130 ° C. when fractionated with TREF, having a block index of at least 0.5 and up to about 1 and a molecular weight distribution M greater than 1.3
a fraction characterized by having w / Mn, and / or

(G) Average block index greater than zero up to 1.0 and molecular weight distribution greater than 1.3, Mw / Mn. The olefin block copolymer is one of the characteristics (A) to (G),
You may have some, all, or any combination. The block index may be measured as described in US Pat. No. 7,608,668, which patent is hereby incorporated by reference for that purpose. An analysis method for measuring the characteristics (A) to (G) is, for example, US Pat. No. 7,608,668, column 31, line 26 to third.
Disclosure at column 5, line 44, which patent is incorporated herein by reference for that purpose.

Suitable monomers used in preparing the OBC of the present invention include ethylene and one or more additional polymerizable monomers other than ethylene. Examples of suitable comonomers include
Propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4
-Methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-
Linear or branched α-olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene;
Cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene and the like, the carbon atom is 3 to 30, preferably 3
20 cyclo-olefins;
Butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,
6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-
Such as methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene,
Diolefins and polyolefins; and
3-phenylpropene, 4-phenylpropene, 1,2-difluoroethylene, tetrafluoroethylene, and 3,3,3-trifluoro-1-propene,
Is mentioned.

The olefin block copolymer is 0.820 g / cc to 0.925 g / cc, or 0
. It has a density of 860 g / cc to 0.88 g / cc, or 0.860 g / cc to 0.879 g / cc. OBC is 40 to 70, preferably 45 to 65, more preferably 50 to
Has a Shore A value of 65. In some embodiments, the olefin block copolymer is from 0.1 g / 10 min as measured by ASTM D1238 (190 ° C./2.16 kg)
30 g / 10, or 0.1 g / 10 min to 20 g / 10 min, or 0.1 g / 10 min to 15 g
It has a melt index (MI) of / 10 minutes. The olefin block copolymer is 5
% To 45% by weight, preferably 10% to 30% by weight, more preferably 10% by weight
Present in an amount of ˜25% by weight. The composition may comprise more than one olefin block copolymer.

The olefin block copolymer can be produced by a chain transfer process as described in US Pat. No. 7,858,706, which is hereby incorporated by reference. In particular, suitable chain transfer agents and related information can be found in column 16, line 39-
It is listed in the 19th column and the 44th line. Suitable catalysts are described in column 19, line 45 to column 46, line 19, and suitable promoters are described in column 46, line 20 to column 51, line 28.
The process is described in various places in the literature, especially in column 51, line 29 to column 54, line 56. The process is also described, for example: US Pat. No. 7,608,668,
US 7,893,166 and US 7,947,793.

The olefin block copolymer may be a reaction product of an ethylene / α-olefin interpolymer and any suitable crosslinker, ie a cross-linked ethylene / α-olefin interpolymer. Thus, the cross-linking agent may be a chemical compound, but is not necessarily so. Cross-linking factors used in this specification also include electron beam irradiation, β-ray irradiation, γ-ray irradiation,
Examples include corona irradiation, silanes, peroxides, allyl compounds, and ultraviolet light, with or without a crosslinking catalyst. US Pat. Nos. 6,803,014 and 6,667,351
No. discloses an electron beam irradiation method used in the embodiments of the present specification. In some embodiments, the percent of cross-linked polymer is at least 10 percent, preferably at least about 20 percent, more preferably at least about 25 percent to about 75 percent, preferably measured by weight percent of the gel formed. Up to about 50 percent. Usually, as the amount of crosslinking increases, the ignition resistance of the composition increases.

The terms “propylene-ethylene-interpolymer”, “propylene-based polymer” or “propylene-based plastomer or elastomer (PBPE)” generally refer to a copolymer comprising propylene and a monomer such as ethylene. Preferably, propylene comprises the largest molar fraction of the entire polymer, i.e. propylene comprises at least about 70, preferably at least about 80, more preferably at least about 90 mole percent of the total polymer, with a substantial remainder of the total polymer being It contains at least one other comonomer, preferably ethylene. Suitable propylene-ethylene interpolymers are described, for example, in WO 2006/115839 published Nov. 2, 2006, which is hereby incorporated by reference. Suitable propylene-ethylene interpolymers are The Do
Exxon as VERSIFY (trademark) from w Chemical Company
VISAMAXX ™, LICOCENE ™ polymer (Clarian)
t), EASTOFLEX ™ polymer (Eastman Chemical Co
. ), REXTAC ™ polymer (Hunstman), and VESTOPLAST
It is commercially available as (trademark) polymer (Degussa). Other suitable polymers include propylene-α-olefin block copolymers and interpolymers known in the art, as well as other propylene-based block copolymers and interpolymers.

Preferably, the propylene-based polymer is 230 ° C / 2.
A range of 0.01 to 2000 g / 10 min measured at 16 kg, more preferably 0.1 to 10
It has a melt flow rate (MFR) in the range of 00 g / 10 min, more preferably 0.5-500 g / 10 min, even more preferably 1-100 g / 10 min.

In another embodiment, the propylene-based polymer is 230 ° C / in accordance with ASTM D1238.
The range of 0.01 to 300 g / 10 min measured at 2.16 kg, more preferably 0.1 to 2
In the range of 00 g / 10 min, more preferably 0.5-100 g / 10 min, or 1-50 g / 1
It has a melt flow rate (MFR) of 0 minutes. All individual values and subranges from 0.01 to 300 g / 10 min are included herein and disclosed herein.

The propylene-based polymer used in the present invention may have any molecular weight distribution (MWD). MWD broad or narrow propylene-based polymers are formed by means in the art. Propylene-based polymers with narrow MWD are conveniently reactor graded by visbreaking or using a single site catalyst.
rad) (not visbreaking) or by both methods.

Propylene-based polymers can be reactor grade, visbreaking, branched or coupled to provide increased nucleation and crystallization rates. In this specification,
The term “coupled” is used to refer to a rheology-modified propylene-based polymer that exhibits a change in the resistance of the molten polymer and flows upon extrusion (eg, in an extruder just before in a circular mold). “Vis-broken” is intended for chain scission, while “coupled” is intended for cross-linking or networking.
As an example of coupling, after extrusion, a coupling agent (eg, an azide compound) can be used at a relatively high melt flow rate such that after extrusion, the resulting polypropylene polymer composition acquires a melt flow rate substantially lower than the initial melt flow rate. And adding to polypropylene polymer.
Preferably, for coupled or branched polypropylene, subsequent MFR vs. initial M
The FR ratio is 0.7: 1 or less, more preferably 0.2: 1 or less.

Suitable branched propylene-based polymers used in the present invention are, for example, from Basell to P
It is commercially available under the trade names rofax PF-611 and PF-814. Or
Branched or coupled propylene-based polymers are within the skill of the art, for example, US Pat. No. 5,414,027 (use of high energy (ionizing) radiation in a low oxygen atmosphere).
European Patent No. 090889 belonging to Himont (electron beam irradiation of isotactic polypropylene at low temperature); US Pat. No. 5,464,907 (Akzo Nobel);
NV); European Patent No. 0754711 (hydrogen peroxide treatment) belonging to Solvay; and US Patent Application No. 09 / 133,576 (azide coupling agent) filed Aug. 13, 1998, disclosed by DeNicola et al. It can be prepared by means such as peroxide or electron beam treatment. Each of these patents / applications is hereby incorporated by reference.

Usually, the mixture and amount of components in the composition of the invention is such that the compound has the appropriate Tg as determined by DSC and the appropriate density for the desired application. For applications such as signboards, tablecloths, sagging fabrics, medical or surgical sanitary fabrics, bandages, wound dressings, etc., typical Tg is about −10 ° C. to about 50 ° C., more preferably about ca. 0 ° C to about 40 ° C. Similarly, the density should be appropriate for the desired application. For such applications, a suitable density of the composition is often about 0.5 g / cm ³ to about 5 g / cm ³ , preferably about 0.75 g / c.
m ³ to about 3 g / cm ³ , more preferably about 1 g / cm ³ to about 2 g / cm ³ . The polymer, tackifier, and filler may be mixed by any convenient method, but are usually mixed, for example, in a Bamburi mixer or a twin screw extruder. Alternatively, the components may be formulated using a solvent suitable for dissolving the polymer and tackifier component. If combined with the filler prior to removal of the solvent, the composition of the present invention can be produced as well.

The amount of polymer or mixture of polymers will vary depending on the type of polymer, the desired application, properties, and other factors of the application. Usually, the weight ratio of tackifier to total polymer is at least about 0.1, preferably at least about 0.15, more preferably at least 0.2 to
At most about 4, preferably at most about 3, more preferably at most about 2. Often, affine deformation is achieved with about 35 weight percent to about 90 weight percent, more preferably about 40 to about 85, more preferably about 40 weight percent to about 82 weight percent polymer based on the weight of polymer and tackifier. I know I can do it. In some embodiments, the olefin block copolymer (A) versus the propylene-based polymer (B
) Weight ratio is from about 10: 1 to about 1: 1. In some embodiments, the composition has a normalized retained load percentage after stress relaxation (condition B, at ambient conditions) of about 20 or greater. In some embodiments, the composition has a normalized retained load percentage after stress relaxation (condition B
(Under ambient conditions) about 20 to about 50, thermal resistance measured at peak melting point about 40 ° C. to about 120 ° C.
This is a thermoplastic composition. In some embodiments, the filler comprises from about 1 to about 90 weight percent of the composition, based on the total weight of the composition. In some embodiments, the filler comprises 40 to about 75 weight percent of the composition, based on the total weight of the composition, and the filler is aluminum hydroxide, magnesium hydroxide, decabromodiphenyl oxide, tetradecabromo- A flame retardant filler selected from the group consisting of diphenoxybenzene, ethane-1,2-bis (pentabromophenyl), ethylenebis-tetrabromophthalimide, and mixtures thereof.

In some embodiments, (A) an ethylene / α-olefin multiblock interpolymer, (B) a propylene-based polymer or elastomer, or (C) (A) and (B
) Mixture of other polymers, such as AFFINITY® or ENGA
Random ethylene copolymers such as GE (registered trademark), HDPE, LLDPE, ULDPE
Traditional polyethylene such as LDPE, homopolymer PP, random copolymer P
It further includes a propylene polymer such as P or PP plastomer / elastomer, or a combination thereof. The amount of such other polymers will vary depending on the desired elasticity and compatibility with the particular ethylene / α-olefin interpolymer used.

Composition Tackifiers Tackifiers that may be useful in the present invention vary depending on the application. Usually, however, it is any adhesive that is compatible with the polymer to achieve the desired properties, such as stress relaxation, compatibility and / or drapeability, and is a replacement for PVC in a given formulation. An imparting agent may be used. While suitability may be measured by routine experimentation, often useful tackifiers may exhibit one or more of the following properties: a glass transition temperature of about 40 ° C. to about 95 ° C., about 100 ° C. to about 160 ° C. ring and ball softening point, or about 0.5 g / cm ³ to about 1
. A density of 5 g / cm ³ . Thus, in contrast to PVC formulations that require a plasticizer and need to lower the glass transition temperature of the composition, suitable tackifiers often increase the glass transition temperature of the compositions of the present invention. Suitable tackifiers are selected from the group consisting of rosins, modified rosins, rosin esters, aromatic modified alicyclic hydrocarbon resins, aliphatic petroleum hydrocarbon resins, partially hydrogenated aliphatic resins, terpene resins and mixtures thereof. May be. Suitable tackifier resins are selected from alicyclic hydrocarbon resins, partially hydrogenated hydrocarbon resins and mixtures thereof. Olefin block copolymer (OBC) compatible tackifiers are often hydrogenated rings, 2
Mw less than 500 g / mol, low polarity, and / or aromaticity. The cloud point test measures the temperature at which the resin begins to precipitate from the solvent. Cloud point measurements in various solvents
As an indicator of polarity and aromaticity, thus for example as an indicator of compatibility with OBC. The mixed methylcyclohexane-aniline spot test measures aromaticity and a low value indicates a high aromatic content. The DACP (diacetone alcohol cloud point) test measures polarity. A low value indicates a large polarity. For OBC compatibility, tackifiers with DACP values of about 40 ° C. to about 80 ° C. and MMAP values of about 70 ° C. to about 90 ° C. are often preferred.

The amount of tackifier will vary depending on the other ingredients and the desired application. In general, increasing the amount of tackifier in the composition decreases the tensile strength and / or elongation of the composition. On the other hand, decreasing the amount of tackifier increases elastic recovery and decreases stress relaxation. Although not intending to be limited by theory, the parameter known to correlate with various properties is the glass transition temperature (Tg).

The scientific community has developed theories and equations that can be used to predict the relationship between glass transition temperature (Tg) and composition. For example, the well-known Fox equation below may be useful in predicting the glass transition temperature of a mixture of polymers with various glass transition temperatures:
It can be used with polyolefins (with known glass transition temperatures) to predict the amount of tackifier (with known glass transition temperatures) that can achieve the desired Tg of the mixture.

Where
T _g is the glass transition temperature of the mixture;
T _ga glass transition temperature of component A, w _a is the weight fraction of component A in the total polymer fraction in the mixture;
T _gb is the glass transition temperature of component B, w _b is the weight fraction of component B in the total resin fraction in the mixture,
It is.

Alternatively, other equations such as the Gordon-Taylor equation can be used. It should be recognized that polymer theory for describing polymer properties will undergo further progress and refinement. It is also my claim that recognizing the theory is not intended to limit the novel composition of the present invention.

Composition Filler The amount and amount of filler will vary depending on the other ingredients, amount and desired application. For example, if flame retardancy or high temperature performance is desired, halogenated fillers can be useful as described further below. Normally, the filler is ammonium polyphosphate, magnesium hydroxide, calcium hydroxide, alumina trihydrate (also called aluminum trihydroxide), calcium carbonate, glass fiber, marble dust, cement dust, clay, feldspar, silica, diatomaceous earth, Talc or glass, fumed silica, silicate, alumina, magnesium oxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium oxide, glass particles, mica, clay, wollastonite, and chalk Selected from the group consisting of

Suitable flame retardant fillers are materials that block the flame or resist the spread of the flame.
In terms of this performance, alongside natural substances such as asbestos, usually halocarbons such as polybrominated diphenyl ether (PBDE), polychlorinated biphenyl (PCB) and chlorendic acid derivatives, most often dibutyl chlorendate and dimethyl chlorendate Synthetic materials such as have also been used. In general, the following grades of flame retardant compounds are most common: aluminum hydroxide, magnesium hydroxide and various hydrates; organic bromine and organic chlorine; organic phosphates, phosphorus halides and red phosphorus Forms of phosphorus; antimony trioxide; and boron compounds, mostly borates. Tetrakis (hydroxymethyl) phosphonium salt produced by passing phosphine gas through a solution of mineral acid such as formaldehyde and hydrochloric acid is used as a flame retardant for textiles. Other flame retardants include chlorinated paraffin, polybrominated biphenyl (PBB), pentabromodiphenyl ether (penta BDE), octabromodiphenyl ether (octa BD).
E), decabromodiphenyl ether (deca BDE), hexabromocyclododecane (H
BCD), tri-o-cresyl phosphate, tris (2,3-dibromopropyl) phosphate (T
RIS), bis (2,3-dibromopropyl) phosphate, tris (1-aziridinyl) -phosphine oxide (TEPA), and the like. Particularly preferred flame retardant or high temperature heat resistant fillers that are often compatible with polyethylene include Albemarle Corporation.
aluminum hydroxide, magnesium hydroxide, decabromodiphenyl oxide, tetradecabromo-diphenoxybenzene, ethane-1,2-bis (pentabromophenyl), ethylene bis-tetrabromophthalimide, and mixtures thereof commercially available from Ion Is mentioned.

The amount of filler varies depending on the application. Typical amounts are about 0, preferably 1 to about 90 weight percent, preferably about 5 to about 80 weight percent, more preferably about 15 weight percent to about 0, based on the total weight of the composition. A range of about 70 weight percent, most preferably about 40-75 weight percent filler. In some embodiments comprising a composition of the invention in a coextruded structure, at least one surface layer is
1-75% filler, more preferably 10-50% by weight, most preferably 10-40% by weight filler. In bicomponent fibers, at least one portion of the fibers on the surface is 1-75% filler, more preferably 10-50% by weight, most preferably 10-4.
Contains 0 wt% filler.

Additives Other ingredients that may be useful in the compositions of the present invention include, for example,
(1) at least one metal borate selected from group IIA metal borates;
And optionally polydimethylsiloxane, organopolysiloxane, tartaric acid, stearic acid,
About 0. 0 selected from the group consisting of zinc stearate, wax, and high melt flow rate polyolefin.
5 to about 10 weight percent of at least one processing aid;
(2) at least one initiator or at least one coupling agent selected from the group consisting of organic peroxides, silanes, titanium, zirconium acid, multifunctional vinyl compounds and organic azides;
(3) at least one hindered amine stabilizer;
Is mentioned. Still other additives include coupling agents such as those selected from the group consisting of maleic anhydride, hydroxylamine or epoxy modified polyolefins, and
Transition metal stearic acid such as zinc stearate
Wetting agents such as those selected from the group consisting of (earates).

Composition Properties The composition has been found to be widely used in a variety of applications, and the composition properties vary depending on the application in which it is formulated. In general, the composition provides desired properties such as stress relaxation, suitability, drapeability, and / or ignition resistance. The details vary depending on whether the formulation is designed to be used, for example, as a sign, tablecloth, sagging fabric, medical or surgical sanitary fabric, bandage, and wound dressing.

In some embodiments, the composition has one or preferably one or more of the following properties: compatibility with stress relaxation properties, compatibility with crease properties, and compatibility with affine deformations. Cast film, blown film, or calendering process
processability by one or more processing processes including ing processes); be easily and cleanly tearable by hand; and be film compatible with additives. In fiber or nonwoven applications, the composition typically has one or more of the following properties: made in a manner known in the art, the resulting article has at least one of the following properties: : Compatibility with stress relaxation properties and crease properties; melt spun, solvent spun, staple fiber, spunbond,
Processability by one or more processing processes including meltblown, or combinations thereof;
It must be easily and cleanly tearable by hand; and must be film compatible with the additive.

Test Methods The following analytical techniques are used in the following examples: Standard CRYSTAF method.

Standard CRYSTAF Method Branch distribution is measured by crystallization analysis fractionation (CRYSTAF) using a CRYSTAF200 unit commercially available from PolymerChar, Valencia, Spain. Samples are dissolved in 1,2,4 trichlorobenzene at 160 ° C. (0.66 mg / mL) for 1 hour and stabilized at 95 ° C. for 45 minutes. Sampling temperature is 0.2 ° C /
The range is 95 to 30 ° C. with a cooling rate of minutes. The polymer solution concentration is measured using an infrared detector. The cumulative soluble concentration is measured as the polymer crystallizes while the temperature decreases.
The analytical derivative of the cumulative profile reflects the short chain branching distribution of the polymer.

CRYSTAF peak temperature and area are measured using CRYSTAF software (Version 2
001. b, PolymerChar, Valencia, Spain). The CRYSTAF peak finding routine identifies the peak temperature as the maximum value in the dW / dT curve and as the area between positive maximum inflections on either side of the peak identified in the derivative curve. In order to calculate the CRYSTAF curve, the preferred processing parameters have a temperature limit of 70 ° C., a smoothing parameter that is above the temperature limit by 0.1 and below the temperature limit by 0.3.

DSC Standard Method Differential scanning calorimetry results are determined using a TAI model Q1000 DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml / min is used.
The sample is compressed into a thin film, melted in a press at about 175 ° C., and then air cooled to room temperature (25 ° C.). 3-10 mg of material is then cut into a 6 mm diameter disc, accurately weighed, placed in a lightweight aluminum pan (approximately 50 mg), and then crimped
shut). The thermal behavior of the sample is investigated with the following temperature profile. Sample 18 rapidly
Heat to 0 ° C. and hold isothermal for 3 minutes to remove previous thermal history. Sample then
Cool to 40 ° C. at a cooling rate of 10 ° C./min and hold at −40 ° C. for 3 minutes. Then sample 1
Heat to 50 ° C. at a heating rate of 10 ° C./min. Record the cooling curve and the second heating curve.

The DSC melting peak is measured as the maximum heat flow rate (W / g) with respect to a linear baseline drawn between −30 ° C. and the end of melting. The heat of fusion is measured as the area under the melting curve between −30 ° C. and the end of melting using a linear baseline.

GPC Method GPC Gel Permeation Chromatography System is a Polymer Laborato
ries Model PL-210 or Polymer Laboratories
It consists of any Model PL-220 device. The column and carousel compartment are operated at 140 ° C. Three Polymer Laboratories 10 micron Mixed-B columns are used. The solvent is 1,2,4 trichlorobenzene.
Samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly at 160 ° C. for 2 hours. The injection volume used was 100 microliters and the flow rate was 1.
0 ml / min.

Calibration of the GPC column set has molecular weights ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures with at least 10 separations between each molecular weight.
Perform with one narrow molecular weight distribution polystyrene standard. Standard is Polymer Labora
Buy from tories (Shropshire, UK). The polystyrene standard is 1,
For a molecular weight solvent over 000,000, it is 0.025 grams in 50 milliliters,
And for solvents with a molecular weight of less than 1,000,000, it is prepared at 0.05 grams in 50 milliliters. The polystyrene standard is dissolved at 80 ° C. with gentle agitation for 30 minutes. Narrow standard mixtures are run first and in order of decreasing highest molecular weight components to minimize degradation. Polystyrene standard peak molecular weight is converted to polyethylene molecular weight using the following formula (Williams and Ward, J. Polym. Scl, Polym. L).
et. 6, 621 (1968)): M polyethylene = 0.431 (
M polystyrene).

Polyethylene equivalent molecular weight calculation (equivalent molecular weight)
ht calculatoin) is a Viscotek TriSEC software Ve
This is performed using rsion3.0.

Compression Set Compression set is measured according to ASTM D 395. The sample is 3.2 mm thick,
A round disk with a diameter of 25.4 mm with a diameter of 2.0 mm and 0.25 mm has a total thickness of 12.7 m
Prepare by stacking until m is reached. The disc must be hot-pressed under the following conditions:
Zero pressure at 90 ° C. for 3 minutes, later 86 MP at 190 ° C. for 2 minutes, followed by 86 MPa in the press
Cut out from a 12.7 cm × 12.7 cm compression molded plaque molded under cooling with cold running water.

Density Samples for density measurement are prepared according to ASTM D1928. Measurement is ASTM D
792, using method B, with a sample press within 1 hour.

Flexural modulus / secant modulus / storage modulus Samples are compression molded using ASTM D1928. The flexural modulus and 2 percent secant modulus are measured according to ASTM D-790. Storage modulus is ASTM D5
Measure according to 026-01 or equivalent technique.

Mechanical properties—tensile, hysteresis, stress relaxation, crease and tear Stress-strain behavior in uniaxial tension is measured using ASTM D1708 microtensile specimens. Samples are stretched using an Instron at 21O < ⁰ > C at 500% min- ¹ . The tensile strength and elongation at break are reported from the average of 5 specimens.

100% and 300% hysteresis is ASTM D1 with Instron ™ equipment.
Determined from cyclic loads up to 100% and 300% strain using a 708 micro tensile specimen. The sample is loaded and unloaded at 21 ° C. for 3 cycles, 267% min− ¹ . 300%
And cycle experiments at 80 ° C. are performed using an environmental chamber. For the 80 ° C. experiment, equilibrate the sample for 45 minutes at the test temperature before testing. In the 21 ° C., 300% strain cycle experiment, the shrinkage stress at 150% strain from the first unloading cycle is recorded. The percent recovery for all experiments is calculated from the first unloading cycle using the strain where the load returns to baseline. Recovery percentage is

(Where ε _f is the strain taken against the cycle load and ε _s is the strain when the load returns to baseline during the first unloading cycle)
Is defined as

Stress relaxation is measured for 12 hours at 50 percent strain and 38 ° C. using an Instron ™ instrument with an environmental chamber. The shape of the gauge is 76 mm × 25 mm × 0.
4 mm. After the intended temperature of the application (ie, ambient temperature, 37 ° C., etc.) is equilibrated in the environmental chamber for 45 minutes, the sample is subjected to the desired target stress and rate of the application (ie, Condition A: 3
(50% strain at 33% min- ¹ and condition B: 100% strain at 500% min- ¹ ). The stress was recorded as a function of time for the application specific test period (ie, 5 minutes, 12 hours), defined as the end of the test. The percentage of stress relaxation is the formula:

(Where L ₀ is the load of the target strain at 0 o'clock and L _end is the load at the _end of the test).

A simple test of crease properties is performed by creasing the film at 180 ° at ambient temperature and then measuring the angle at which subsequent creases open. The lower or smaller the angle, the better because it indicates a higher crease retention.

Tensile notched tear exper
are performed on a sample having a density of 0.88 g / cc or less using an Instron ™ instrument. This shape consists of a gauge portion of 76 mm × 13 mm × 0.4 mm, and this sample has a 2 mm cut at half the length of the test piece. Stretch at 508 mm min- ¹ at 21 ° C. until the sample breaks. This tear energy is calculated as the area under the stress-elongation curve up to the strain at the maximum load. Report the average of at least 3 specimens.

TMA
Thermal Mechanical Analysis (Penetration Temperature) was formed at 180 ° C. and 10 MPa molding pressure for 5 minutes and then rapidly cooled with wind 3
This is done with a compression molded disk having a diameter of 0 mm × 3.3 mm. The equipment used was Perkin-
TMA7, a trademark available from Elmer. In this test, a probe with a 1.5 mm radius tip (P / N N519-0416) is applied to the surface of the sample disk with a force of 1N. The temperature is increased from 25 ° C to 5 ° C / min. This probe penetration distance is measured as a function of temperature. The experiment ends when this probe has penetrated 1 mm into the sample.

DMA
Dynamic Mechanical Analysis (DMA
) Is measured on a compression-molded disc molded in a hot press at 180 ° C. and a pressure of 10 MPa for 5 minutes and then water-cooled in this press at 90 ° C./min. The test consists of an ARES controlled strain rheometer (TA in) with a double cantilever fixture for torsion testing.
instrument).

A 1.5 mm plaque is pressed and cut into bars measuring 32 × 12 mm. The sample was clamped at both ends between fixtures separated by 10 mm (grip interval ΔL),
Subject to successive temperature steps from −100 ° C. to 200 ° C. (5 ° C. per step). At each temperature, the torsional modulus G ′ is measured at an angular frequency of 10 rad / s and this strain amplitude is zero to ensure that the torque is sufficient and that the measurement remains in a linear state. Maintained between 1 percent and 4 percent.

The initial static force of 10 g is maintained (automatic pulling method) to prevent loosening in the sample when thermal expansion occurs. As a result, the grip spacing ΔL increases with temperature, particularly above the melting or softening point of the polymer sample. The test was conducted at a maximum temperature or 6 gaps between fixtures.
It ends when it reaches 5mm.

Melt Index Melt index _{I 2} is, ASTM D1238, measured according to the conditions 190 ° C. / 2.16 kg. Melt index I ₁₀ is also ASTM D1238, condition 190 ° C
Measure according to / 10 kg.

ATREF
Analytical temperature rising elution fractionation (analytical temperature rising fractionation)
elution fractionation) (ATREF) analysis is described in US Pat.
798,081 and Wilde, L .; Ryle, T .; R. Knobeloch,
D. C. Peat, I .; R. ; Determination of Branchin
g Distributions in Polyethylene and Ethy
len Copolymers, J.A. Polym. Sci. , 20, 441-455 (
1982), the entirety of which is hereby incorporated by reference. The composition to be analyzed is dissolved in trichlorobenzene and dissolved at 0.1 ° C /
Crystallize in a column containing an inert support (stainless steel shot) by slowly lowering the temperature to 20 ° C. with a cooling rate of minutes. This column is equipped with an infrared detector. An ATREF chromatographic curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 to 120 ° C. at a rate of 1.5 ° C./min. .

¹³ C NMR analysis Samples are prepared by adding about 3 g of a 50/50 mixture of tetrachloroethane-d ² / orthodichlorobenzene to a 0.4 g sample in a 10 mm NMR tube. The sample is melted and homogenized by heating the tube and its contents to 150 ° C. JEOL ECLIPSE, corresponding to a ¹³ C resonance frequency of 100.5 MHz
(Trademark) 400 MHz spectrometer, or Varian Unity Plus (trademark) 400
Data is collected using a MHz spectrometer. The data is obtained using 4000 transients per data file with a 6 second pulse repetition time delay. Add multiple data files together to achieve the minimum signal-to-noise ratio for quantitative analysis. The spectral width is 25,000 Hz and the minimum file size is 32K data points. This sample is analyzed at 130 ° C. in a 10 mm broadband probe. Comonomer incorporation is determined by Randall's triad method (Randall, JC; JM
S-Rev. Macromol. Chem. Phys. , C29, 201-317 (19
89), which is incorporated herein by reference in its entirety.

Polymer fractionation by TREF Large-scale TREF fractionation is performed by dissolving 15-20 g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring at 160 ° C. for 4 hours. This polymer solution is 30-40 mesh (600-425 μm) spherical technical quality glass beads (Potters Industries, HC30 Box 20, B
commercially available from rowwood, TX, 76801) and 0.028 "(0.7 mm) diameter stainless steel cut wire shot (Pellets, Inc. 63 Industr)
3 inches × 4 feet (7.6 cm × 12 cm) packed with a 60:40 (v: v) mixture of ial Drive, North Tonawanda, NY, 14120.
) With a 15 psig (100 kPa) nitrogen. The column is immersed in a thermally controlled oil jacket initially set at 160 ° C. This column is first 12
Cool ballistically to 5 ° C, then slowly cool to 20 ° C at 0.04 ° C per minute,
Hold for hours. While increasing the temperature at 0.167 ° C. per minute, fresh TCB was reduced to about 65
Introduce in ml / min.

Approximately 2000 ml of eluent from the preparative TREF column is collected in a 16-station heated fraction collector. The polymer is concentrated in each fraction using a rotary evaporator until about 50-100 ml of polymer solution remains. The concentrated solution is allowed to stand overnight, after which excess methanol is added, filtered and rinsed (approximately 300-500 ml of methanol including the final rinse). The filtration step was performed using 5.0 μm polytetrafluoroethylene coated filter paper (commercially available from Osmonics Inc.,
Performed in a 3-position vacuum assisted filtration station using catalog number Z50WP04750). The filtered fraction is dried in a vacuum oven at 60 ° C. overnight and weighed on an analytical balance before further testing.

Melt Strength Melt strength (MS) is measured by using a capillary rheometer fitted with a 2.1 mm diameter 20: 1 die with an entrance angle of about 45 degrees. After equilibrating the sample for 10 minutes at 190 ° C., the piston is operated at a speed of 1 inch / minute (2.54 cm / minute). The standard test temperature is 190 ° C. Samples are companding uniaxially to a set of accelerating nips located under 100mm the die with an acceleration of 2.4 mm / sec ^2. The required tension is recorded as a function of the nip roll take-up speed. The maximum tension reached during the test is defined as the melt strength. In the case of polymer melting exhibiting take-up resonance, the tension before occurrence of take-up resonance was taken as the melt strength. Melt strength is recorded in centinewton (“cN”).

Stress relaxation recovery behavior of the composition at 100% applied strain. This test is based on International Publication No. WO1992 / 020534 and International Publication No. WO2002 /
No. 064674, previously used as a measure of film compatibility. In this test, ASTM D1708 dog-bone micro-te
nsile) Samples are cut from compression molded or extruded sheets. Step 1 of this test
The sample is stretched to 100% strain with an Instron at a rate of 500% / min. In step 2, the sample is properly held at 100% strain for 5 minutes, during which time the stress is relaxed. At the end of 5 minutes, as step 3, the film is shrunk with the crosshead reversed and the recovery or permanent set is measured. The stress at time t is normalized by the stress at the beginning of the stress relaxation step and is plotted as a function of time over 5 minutes to monitor the fraction of retained load.

Tensile Strength and Elongation Tensile strength and elongation at break were measured according to ASTM D1708 using an Instron 5564 fitted with a 1 kN capacity load cell and an air operated grip. 500%
A strain rate of / min was used.

25% Hysteresis Test A hysteresis test was performed using ASTM D1708 microtensile samples. The test piece was stretched to 25% strain and returned to 0% strain for 2 cycles at 100% / min. Permanent set was defined as the occurrence of a positive load during stretching in the second cycle. This method was adopted from the test method described in WO9220534.

Example 1-Compositions suitable as strips Formulations AD are made by blending the components in the amounts shown in the table below. A bamburi mixer is used for blending. After compounding, the compound is extruded as a strip in a 3/4 "single screw Haake extruder using a 4" wide coat hanger die.

VERSIFY 2200, VERSIFY 2300 and DE2400.01 are the the
P / E elastomers and plastomers commercially available from Dow Chemical Company. Escorez 56 commercially available from Exxon Mobil
The 00 series tackifier is a very lightweight colored aromatic modified alicyclic hydrocarbon resin. E
scorez5637 was chosen because of its high softening point and known compatibility with polyethylene polymers.

OBC1 is an INFUSE 9100 olefin block copolymer commercially available from The Dow Chemical Company and has a melt index of 1.0.

Holding load versus time, recovery from shrinkage as measured by the stress relaxation recovery method discussed above, stress versus strain, and hysteresis were measured for formulations AD. These are 3M Super
Comparison with r88f-PVC strips. The results are shown in FIGS. The results show that the formulation can be comparable or better than bands made of materials such as f-PVC.

Specifically, FIG. 1 shows the current f-PVC at ambient conditions (about 21 ° C., 50% relative humidity).
The control (3MSsuper88) shows the normalized stress for 5 minutes and the sample is 100% at 500% / min.
% Strain and monitor stress relaxation for the next 5 minutes. Four formulations of the present invention (A
-D) all show similar stress relaxation properties for the object. The retention load fraction of the four formulations over 5 minutes is 0.4, approximately equal to the f-PVC control. The film is shrunk with the crosshead reversed and FIG. 2 shows its permanent set. The higher the permanent set, the smaller the recovery and the lower the tendency to debond. In contrast, neat polyethylene copolymers are often 65%, 35% and 2% on 9, 12 and 15 wt% ethylene containing samples.
It has a permanent strain of 0% and usually shows a retained load fraction close to 0.6.

In addition, the f-PVC coating undergoes affine deformation and is constricted in the stress-strain curve (n
It does not show the behavior of etching and yielding. FIG. 3 shows DP2200.
. It shows that formulations A and B based on 01 and DE 2300.01, respectively, have a yield point and cause uneven deformation. Some applications using f-PVC can tolerate the yield point, but more information should be gathered when using formulations that exhibit a yield point in the stress-strain curve. However, formulations based on OBC and DE 2400.01 do not exhibit a yield point and cause uniform affine deformation, which is often an important performance criterion in some applications.
The permanent set measurement in the 25% hysteresis test for f-PVC strips is 4%, but for formulations with DE 2400.01 and OBC it is 5-6%.
This difference is within the normal uncertainty of measurement and may not be statistically significant.
The elongation and shrinkage curves exhibited by pure polyethylene copolymer resins are almost overlapping, which means that lower hysteresis and therefore less compatibility means that polyethylene copolymer and OBC The blend with tackifier and filler, as an advantage, exhibits significant hysteresis similar to the f-PVC strip.

Higher stress relaxation means a greater reduction in the force that the polymer exhibits over time. This is desirable for applications that require greater compatibility. Typical examples include signboards, sagging cloths, bandages, protective covers, pouches, intravenous fluid-containing bags (intr)
avenue liquid continging bags), floor coverings and tiles.

Example 2-Composition Suitable for Ignition Resistance Applications Formulations 1-4 are made by blending the ingredients in the weight percentages shown in the table below. A bamburi mixer is used for blending. After blending, the blend is pelletized using an underwater pelletizer and 5
Compression molding to a thickness of ~ 7 mils. Set the compression molding machine to 175 ° C and pressure 2000p
3 minutes at si, followed by 50,000 psi for 8 minutes, 15 ° C., 50,000 psi at 1
Cooled for 2 minutes. Some of this sheet with a constant thickness of approximately 6 mils is used for physical testing.

Fusbond MN493 is an approximately 1 weight percent maleic anhydride grafted ethylene-octene copolymer commercially available from DuPont, with a density of 0.87 g / cm ³ and a melt index of 1.0 g / 10 min. Zinc stearate is Alfa A
supplied by esar. MB50-002 in pellet form supplied by Dow Corning
Contains 50% of a low ultra high molecular weight polydimethylsiloxane polymer dispersed in density polyethylene (PE). East supplied by Eastman Chemicals
otac * H100R is used as a tackifier. This resin is a partially hydrogenated aliphatic resin and is chosen for its compatibility with OBC. Eastotac * H100R
Has a glass transition temperature of 44 ° C., a ring and ball softening temperature of 100 ° C., a density of 1.04 g / cc, 4
It has a _{Mn of} 50 g / mol, a _{Mw of} 1050 g / mol. OBC2 is The Do
w INFUSE 9100 olefin block copolymer, commercially available from Chemical Company, having a 0.5 melt index.

Stress versus strain curves, retained load fraction, recovery from shrinkage, and hysteresis are measured for Formulations 1-4 using methods such as those described above. The results are shown in FIGS. Result is,
Formulations 1 and 2 exhibit better stress relaxation, similar recovery and permanent set, while at the same time having acceptable tensile strength and elongation for most of the disclosed applications.

Example 3-Compositions Suitable for Ignition Resistant Applications Comprising LDPE or Modified Olefin Multiblock Interpolymer Formulations 5-10 are made by blending the ingredients in the weight percentages shown in the table below. A bamburi mixer is used for blending. After blending, the blend is pelletized using an underwater pelletizer.

A rheology modified OBC sample was first prepared with a 0.5 MI OBC OBC2 and a high melt strength random copolymer polypropylene DOW DS6D82 with MFR of 5.7 wt% ethylene and 7 (2.16 kg, 230 C) at 70:30. Mix in ratio, then
1500 ppm peroxide Trigonox 101 and 1500 ppm crosslinking aid SR35
Prepare by chemically modifying the blend with 0. This rheology modified OBC is found to have a melt strength of 21 cN at 190 ° C.

AMPLIFYGR216 is an approximately 0.8 wt% maleic anhydride grafted ethylene-octene copolymer commercially available from Dow with a density of 0.87 g / cm ³ and 1.0 g
It has a melt index of / 10 minutes.

All Formulations 5-10 of Example 3 have similar stress relaxation, tension and hysteresis properties as Formulation 1 of Example 2 described above. FIG. 9 shows formulations 1 and 2 of Example 2
And melt strength is compared with the blends 5-10. Compared to Formulation 1 of Example 2 using OBC1 with a melt strength of 4 cN, Formulations 5, 6 and 8 using LDPE / rheology modified OBC compounds have melt strength values of 5 cN, 7 cN and 9 cN, respectively. Bring. 7 cN
Compared to formulation 2 of Example 2 using OBC2 having a melt strength of:
Illustrating melt strength values of 9 cN and 10 cN, respectively. 1.7 times improvement in melt strength of formulation 6 over formulation 1 of Example 2 and about 1 improvement of formulation 9 over formulation 2 of Example 2
. Based on 5 times, Formulations 6 and 9 are considered better for applications that require higher melt strength. These results show that if necessary, the melt strength can be further improved by adding more LDPE and / or modified olefin multi-block interpolymers.

Example 4-Combustion Performance The combustion performance of Formulations 1, 3 and 4 of Example 2 and Formulations 5, 7, 9 and 10 of Example 3 are measured using a corn calorimeter. A cone calorimeter is one of the commonly used types of combustion test equipment that provides quantitative data on the flammability of a material under a constant external heat flow. Flammability is measured by the heat release rate (HRR). As the HRR increases, the flame spreads and the flashover increases. Ignition time, smoke suppression time, total calorific value, CO / CO2 generation and smoke generation are some of the very important data that can be collected from a single cone calorimeter test. Combustion test technology (Fire Testing T
The flammability of plaques compression molded to a thickness of 0.125 "and a size of 10 cm x 10 cm is tested using a technology (FTT) corn calorimeter with a heat flow of 35 kW / m ² . Neither repeated nor triplicate measurements are taken, single combustion data is obtained for each sample for comparison purposes, and the peak exotherm rate (t _peak ) after ignition of the material.
The time taken to reach) is a suitable indicator for comparing samples expressed in terms of burning rate. In this case, the sample with the least amount of tackifier formulation 4 shows the longest time to peak exotherm rate. The sample also burns the longest until smoke extinction. Addition of the silicone masterbatch into Formulation 3 has minimal impact on flammability characteristics. Formulation 1 and Formulations 5 and 7
And the comparison with 9 indicates that the presence of LDPE in the latter formulation appears to stabilize the char structure and slightly reduce the peak exotherm rate. This is evident when comparing the smoke-free time of these samples with Control Formulation 1. The following table lists the ignition time, peak heat generation time, smoke extinguishing time, and peak heat generation rate. Advantageously, these results may be comparable to polyolefin-based non-halogen flame retardant formulations known to those skilled in the art.

Example 5-Variation level of tackifier The formulation is made by blending the ingredients in the weight percentages shown in the table below. The formulation contains a small 25
Use 0 g Haake Bow.

Load vs. strain and normalized stress vs. time and recovery from shrinkage are measured for the above formulations 11-15. The results are shown in FIGS. The result is that the ratio of polymer to tackifier is about 5
It shows the surprising and unexpected property of 0 to about 70%.

For Formulations 11-15, the ratio of LDPE to OBC2 is similar to the filler content,
Although kept approximately constant, changing the amount of tackifier determines the effect of the amount of tackifier on physical properties. The weight fraction of (OBC + LDPE) / (OBC + LDPE + tackifier) is reported as a percentage of polymer in the legend of FIG. FIG. 13 shows formulation 1
1 to 14 show tan δ as a function of temperature compared to Control Formulation 1. The sample with the lowest percentage of polymer (Formulation 14) has a glass transition temperature that changes to room temperature or even f
-It tends to be closest to behavior similar to PVC.

Example 6
Compositions (Table 7) were made using raw materials (Table 6). Show the corresponding mechanical properties (Table 8)
. It should be noted that the surface treated filler (Imers Performance Mi)
selected as filmlink 400) commercially available from generals,
It is calcium carbonate. As can be seen, the formulation of the present invention is a comparative example L ^* (Johnson).
And f-PVC film taken from an f-PVC-based adhesive bandage marketed under the trade name Band-Aid by Johnson Corporation, and higher stress relaxation performance was achieved. Although not limited by theory, it is considered that debonding in which a breathable structure is formed by forming a microcavity when stretched by selecting a surface-treated filler is possible. Such a structure is believed to be advantageous for wound care applications where moisture must be successfully treated to improve skin health.

Claims (11)

A composition suitable as a processed article,
(1) a polymer,
(A) an ethylene / α-olefin multiblock interpolymer;
(B) a propylene-based plastomer or an elastomer,
(C) a polymer selected from the group consisting of: (A) and a mixture of (B);
(2) 1 to 75 weight percent filler based on the weight of the composition;
(3) an effective amount of at least one tackifier;
A composition comprising The composition of claim 1, wherein the composition has a Tg of 0 ° C. to 40 ° C. as measured by DSC. The polymer is an ethylene / α-olefin multiblock interpolymer characterized by 1.7-3.5 Mw / Mn, at least one melting point Tm (° C.), density d (g / cm ³ ), The numerical values of Tm and d are
T _m > −6553.3 + 13735 (d) −7051.7 (d) ²
The composition according to claim 1, which corresponds to the relationship of The ethylene / α-olefin multiblock interpolymer is an ethylene-octene interpolymer comprising at least 50 mole percent ethylene.
A composition according to one or more of the above. 5. A composition according to one or more of claims 1 to 4, wherein the polymer is a propylene-based plastomer or elastomer that is a propylene-ethylene interpolymer comprising at least 80 mole percent propylene. 6. A composition according to one or more of claims 1 to 5, wherein the weight ratio of tackifier to polymer is 0.1-4. 7. A composition according to one or more of claims 1 to 6, wherein the filler comprises 40 to 75 weight percent of the composition, based on the total weight of the composition. The composition according to one or more of the preceding claims, wherein the tackifier has a ring and ball softening point of 100-160 ° C. 9. A composition according to one or more of claims 1 to 8, wherein the tackifier has a glass transition temperature of 40 to 95C. It said tackifier has a density of 0.5 to 1.5 g / cm ^3, the composition according to one or more of claims 1 9. 11. A composition according to one or more of claims 1 to 10, further comprising low density polyethylene.